The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

Abstract

The quantitative conversion of fluorosulfates into trifluoromethyl sulfates is systematically investigated. The reaction proceeds initially according to the general equation[Formula: see text]where E is a coordinatively saturated metal or an organometallic moiety. However, the key to a quantitative substitution is the observed degradation of the SO3F group by excess HSO3CF3 and the noted observation of various volatile by-products that do not appear to interfere in the isolation of analytically pure trifluoromethyl sulfates. The fluorosulfates selected are representatives of the most common bond and coordination types—ionic or covalent with coordination through one, two, or three oxygens of the SO3F groups. The selected substrates display a fairly wide range of solubilities in HSO3F. All conversion attempts are successful except for one, that of polymeric Hg(SO3F)2, and a number of new SO3CF3 derivatives of tin, platinum, germanium, and palladium are described. The solvolysis of tin(IV) acetate in HSO3CF3 is reinvestigated and the syntheses of two other trifluoromethyl sulfuric acid derivatives, CsSO3CF3•HSO3CF3 and CH3CO2H•HSO3CF3, are described.

The system fluorosulfuric acid (HSO3F) and bis(fluorosulfuryl)peroxide (S2O6F2) — a solution study

“…However, these solutions are unstable and slowly give rise to the evolution of heat and volatile products, among them CF30S02F. There is sufficient evidence from the reported interaction of the two acids HS03F and HS03CF3 (26,27) and from the thermal instability of the peroxide (CF3)2S206 (28) to conclude that oxidative cleavage of the S-C bond occurs (29 use of the mixture is only indicated where oxidation reactions proceed rapidly (25).…”

The synthesis and characterisation of hetero-bimetallic sulfonate bridged coordination polymers of the type MIISnIV(SO3X)6 with X = F or CF3

“…The resulting products, like their S03F counterparts, are seemingly insoluble in the parent acid and are usually stable at least up to 300°C. For polymeric Sn(S03CF3)4, depending on the method of preparation lower melting points, 225-227°C (2) and 235°C (15), respectively, are reported.…”

“…A rather sharp medium intensity band at 775 cm-' is found in all spectra. This band is strongly Raman active (2,15) and found in a very narrow frequency range for S03CF3 compounds. Not surprisingly, bands at 640-630 cm-' , attributed predominantly to Sn-0 skeletal vibrations, are found for both series of compounds in the same frequency range with rather similar band shapes and relative intensities.…”

“…More recent work from our laboratory provided additional encouragement: metal oxidation by S2O6F2 in HS03F as solvent represented a simple and facile general route to both Sn(S03F), (13) and Pt(S03F), (14), and the conversion of the more readily accessible fluorosulfates into the corresponding trifluoromethyl sulfates by solvolysis in excess HS03CF3 was systematically explored (15). The preparation of one of the desired bimetallic polymers, ~n " s n ( S o~C F~)~, was quoted as an example (15). The general preparative route, S03X-abstraction (X = F or CF3) by strong acceptors according to: with MIV = Sn or Pt and X = F or CF3 had been explored most recently in attempts to stabilize the divalent cations Sn2+ and ( C H~) , S~~+ in this manner (16).…”

Mass spectrometry and UV‐VIS spectrophotometry of ruthenium(II) [RuClCp(mPTA)2](OSO2CF3)2 complex in solution

“…The stabilization probably occurs because the high chloride level is preventing coordinated chloride exchange in the ruthenium complex I with water, hydroxyl or with trifluoromethylsulfate. 29 In other words, the excess of chloride is blocking ligand exchange of the chloride with water and with other possible ligands in solution. Our results are in agreement with findings for a similar Ru complex with the PTA ligand, where [RuCpCl(PTA) 2 ] and its aqueous parent complex [RuCp(H 2 O)(PTA) 2 ] þ were found to exist in partial equilibrium.…”